N-(sulfonylphenacyl)hexamethylenetetraminium halides



N-(SULFONYLPHENACYIJHEXAMETHYLENE- TETRAMINIUM HALIDES 1 Walter A.'Gregory, Wilmington, Del., assignor to E. I.

du Pont de Nemours and Company, Wilmington, Del, a corporation of Delaware Application February 16, 1953, Serial No. 337,236

6 Claims. (Cl. 260-2485 No Drawing.

This invention relates to N-(organic substituted sulfonylphenacyl)hexamethylenetetraminium halides.

This application is a continuation-in-part of my copending application Serial No. 257,986 filed November 23, 1951.

The N-(organid substituted sulfonylphenacyl)hexamethylenetetramim'um halides of the invention are represented by the formula:

where R1 is a member of the group consisting of alkyl,

halogeno lower alkyl, cyclopentyl, cyclohexyl and vinyl groups having up to 12 carbon atoms or a haloaliphatic radical containing up to 12 carbon atoms, R2 is a member of the class consisting of hydrogen, halogen, lower alkyl and lower alkoxy and X is a halogen of thegroup consisting of chlorine and bromine.

The terms lower alkyl and lower alkoxy as used herein include all alkyl and alkoxy radicals containing not more than-6 carbon atoms.

,Illustrative of the compounds of the invention are:

N [p (chloromethylsulfonyl)phenacyllhexamethylenetetraminium chloride v N 4 p (dichloromethylsulfonyl)phenacyl]hexamethyh N-( p n amylsulfonylphenacyl)hexamethylenetetramin-- 70 N; (P dodecylsulfonylphenacyl)hexamethyleneteraminv ium chloride "ium chloride United States lm 1 7 ing is not, however, an essential feature of the process of i ice N (p cyclohexylsulfonylphenacyl)hexamethylenetetraminium bromide N (o methylsulfonylphenacyl)hexamethylenetetraminium bromide N-(3 methyl-4-methylsulfonylphenacyl)hexamethylenetetraminium bromide N (5 chloro-2-methylsulfonylphenacyl)hexamethylenetetraminium bromide N- (5 isopropylsulfonyl-Z-methoxyphenacyl hexameth'yl- 'enetetraminium bromide The substituted hexamethylenetetraminium halides of the invention can be prepared by reacting an alpha-halosulfonylacetophenone of the formula R2 3) I b-onix where R1, R2 and X have the same significance as in Formula 1, with hexamethylenetetramine in the presence of an organic compound such as, for instance, anisole, ethylidene chloride, or n-butyl chloride.

Anisole is the preferred medium in which to'effect the reaction between a compound .of Formula 2 and hexamethylenetetramine. For optimum yields of desired product the reaction medium shouldbe vigorously agitated.

The preparation of the compounds represented by Formula 2 is fully described and claimed in my copending application, Serial No. 337,237, filed concurrently herewith. In brief, the compounds of Formula 2 are prepared from a compound of the formula where R1 and R2 have the same significance as in Formula 1 by either a process consisting of the steps of acetylation, ha logenation and oxidation, or alternatively, by reacting a compound of Formula 3 with a haloacetyl halide followed by oxidation of the mercapto radical to a sulfonyl group. p

According to the present invention, the reaction between a compound of Formula 2 and hexamethylenetetramine can be effected at normal room temperature. The reaction may also be advantageously effected at slightly elevated temperatures, say, about 40 C. External heatthis invention.

The N (p organosulfonylphenacyl)hexamethylenetetraminium halides of my invention are bactericides and fungicides. They' are also useful in the preparation of synthetic antibiotics.

In order to better understand the invention reference should be had to the following illustrative examples:

Example 1 .Preparation of N p-ethy lsulfonylphenacyl hexamethylenetetraminimum bromide product is suspended in 500 ml. of boiling chloroform. I

The product is filtered hot, collected, washed with 500 ml. of absolute ethanol and then with 500 ml. of ether. The white powder is-N-(p-ethylsulfonylphenacyl)hexamethylenetetraminium bromide, M. P. 169-17 1 C. dec. It has the following structure:

CH2N

Analysis calculated for C1eH2sOaN4SBr: C, 44.55; H,

A mixture consisting of 89 g. of alpha-bromo-p-n propylsulfonylacetophenone, 40.6 g. of hexamethylenetctramine and 750 ml. of anisole is stirred vigorously for a period of three hours. The resulting product is collected by filtration, washed by slurrying twice with 350 m1. of absolute ethanol, then twice with 350 ml. of ether and air-dried.

The Washed product has a melting range of from 155 to 157 C. and smells strongly of anisole which is tenaciously retained. To prepare a sample for analysis a small portion of product is boiled with chloroform. The mixture is filtered and the product collected, cooled and dried. The product of this reaction is N-(p-n-propylsulfonylphenacyl)hexamethylenetetraminium bromide. It has the following structural formula and chemical Analysis calculated for C17H2503N4SB12 N, 12.58; S,

7.20. Found: N, 12.26; S, 6.83.

Example 3.Pre1mrati0n of N-(p-is0pr0pylsulf0nylphenucyl)hcaramel/1ylcnctetraminium bromide Analysis calculated for C12H25O3N4SBI: C, 45.84; H, 10 5.66. Found: C, 45.19; H, 5.60.

Example 4.Preparation of N-(p-n-butylsulfonylphenacyl')hexamethylenetetraminium bromide A mixture consisting of g. of alpha-bromo-p-n- 75 butylsulfonylaeetophenone, 53 g. of hexamethylenetetramine and 400 ml. of anisole is stirred vigorously. A sticky gel begins forming shortly which makes stirring impossible. After the gel stands for a period of one hour, it hardens so that it can be crushed. Stirring of the reaction mixture is continued for a period of two hours. The mixture is filtered. A solid is collected and washed with ether. The solid is an anisole solvate 'of N-(p-nbutylsulfonylphenacyl)hexamethylenetetraminimum bromide, and may be represented by the following formula:

CH: N

Example 5.--Preparation of N-(p-n-amylsulfonylphenacyl)hexamethylenetetraminium bromide A mixture consisting of 44 g. of alpha-bromo-p-namylsulfonylacetophenone, 18.5 g. of hexamethylenetetramine and 600 ml. of n-butyl chloride is shaken vigorously for a period of one and one-half hours. The resulting solid product is collected by filtration, washed with ether and dried, M. P. l12-l22 C. (dec.). The product, N (p n amylsulfenylphenacyl)hexamethylenetetraminium bromide, may be represented by the following formula:

CH2--/-N O CH: O@ H 71C HnS -13 CHzN-CHrN CH; 131'- CH -----N Analysis calculated for C19H2703N4SBIZ N, 11.83.

Found: N, 11.68.

Example 6.Preparati0n of N-(p-dodecylsulfonylphenacyl) hexamethylenetetraminium bromide A mixture consisting of 123 g. of p-dodecylsulfonylphenacyl bromide, 39.9 g. of hexamethylenetetramine and 500 ml. of anisole is shaken vigorously on a mechanical stirrer for a period of one hour. A solid product results. It is collected by filtration, washed twice with ether and dried, M. P. ll3-116 C. (dec.). An analytical sample of the product is purified by boiling with chloroform, cooling, diluting with ether, filtering it from the ether and drying. The sample melts at 1l3116 C. (dec.). The product, N-(p-dodecylsulfonylphenacyl)hexamethylenetetraminium bromide, may be represented by thestructural formula:

Found: N, 9.79.

Example 7.Preparati0n of N (p cyclohexylsulfonylpherzacyl) hexamethylenetetraminium bromide A mixture consisting of 103 g. of alpha-bromo-p-cyclohexylsulfonylacetophenone, 42 g. of hexamethylenetetramine and 420 ml. of anisole is shaken vigorously for a period of two and one-half hours. The reaction mixture is filtered, and a solid is collected, washed twice with 750 ml. of ether and dried, M. P. -172 C. dee. The solid 6 is N-(p-cyclohexylsulfonylphenaoyl)hexamethylenetetra- 2. N (p alkylsulfonylphenacyl)hexamethyleneten'aminium bromide solvated with one molecule of anisole. It minium bromide. has the following structural formula:

OHr----N O C G Q s CH|NCH -N on, Br-camocm 0 Cg: CH N I claim: 3. N (p methylsulfonylphenacyl)hexamethylene- 1. A compound of the formula, tetraminium bromide.

4. N (p halogego lower alkylsulfonylphenacyl)hexa- R: o g 15 methylenetetraminiu'm bromide.

g 5. N (p ethylsulfonylphenacyl)hexamethylenetetrao -cmN-cm-N 0 H! X minium bromide. RPS 6. N [(P trifluoromethylsulfonyl)phenacyHhexa- 0 CH methylenetetraminium bromide.

rN fl' 1 s a mcmbcl 0f the group consisting of l y 20 References Cited in the file of this patent halogeno lower alkyl, eyclohexyl, cyclopentyl and vinyl UNITED STATES PATENTS groups, R: is a member of the class consisting of hydrogen,

halogen, lower alkyl and lower alkoxy radicals, and X 46,762 Long Mar. 27, 1951 is a halogen of the-group consisting of chlorine and bromine. 25 

1. A COMPOUND OF THE FORMULA 